CN105622914B - A kind of preparation method of water-based HDI modified poly esters light-cured resin - Google Patents
A kind of preparation method of water-based HDI modified poly esters light-cured resin Download PDFInfo
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- CN105622914B CN105622914B CN201410720474.3A CN201410720474A CN105622914B CN 105622914 B CN105622914 B CN 105622914B CN 201410720474 A CN201410720474 A CN 201410720474A CN 105622914 B CN105622914 B CN 105622914B
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Abstract
The present invention relates to a kind of preparation method of water-based HDI modified poly esters light-cured resin, consisting of：Hyper-branched polyester 1~3%, the acrylic monomers 5~12% of hydroxyl, HDI trimer 10~16%, dibutyl tin laurate 0.02~0.3%, cis-butenedioic anhydride 12~25%, N, N dimethylanilines 5~10%, sodium hydroxide 3~6%, deionized water 40~60%；Hyper-branched polyester is synthesized by DMPA and TMP under catalyst action；Water-based HDI modified poly esters light-cured resin produced by the present invention, excellent storage stability；Film has excellent water resistance, hardness, resistance to ag(e)ing, resistance toization moral character and stain resistance in the presence of light trigger; also have the characteristics that glossiness is high, wearability is good, adhesive force is strong, richness is high, excellent impact resistance simultaneously, be widely used in the surface emissivity application and protection of the products such as woodenware, metal, kirsite, aluminium alloy, magnesium alloy, plastics.
Description
Technical field
The present invention relates to a kind of preparation method of photocuring polyester resin, more particularly to a kind of water-based HDI modified poly esters
Light-cured resin, belong to synthetic resin technical field.
Background technology
In recent years, environment-friendly type coating includes high solid and solventless coatings, water paint, powdery paints and photocuring apply
Material obtains very fast development.Ultraviolet light solidification has the advantages that fast reaction, ambient operation, low energy consumption and solvent-free of low pollution.
Aqueous photo-curing polyester has super branched molecule structure, and hyper-branched polyester is incorporated into UV curing systems, can overcome line style
Some shortcomings of oligomer, such as film significant shrinkage, diluent volatilization, toxicity are big；Have in waterborne radiation curable coating and represent
Property one of aqueous photo-curing polyester coating, have the characteristics that gloss is high, adhesive force is strong, richness is high, excellent impact resistance, because
This is widely used in the protection of metal and woodenware surface and decoration.
Aqueous hyperbranched polymer has highly branched molecular structure, has very narrow relative molecular mass distribution, with
Dendritic polymer has similar structure, because macromolecular has similar three-dimensional spherical cramped construction, hydrodynamics revolution half
Footpath is small, and the degree of branching is very high, intermolecular not easy entanglement, therefore viscosity is smaller with the increase change of relative molecular mass；And divide greatly
Subband has many functional end groups, there is critically important influence to whole dissaving polymer, can be by being controlled to terminal groups modification
The performance of dissaving polymer processed, such as glass transition temperature and the solubility in different solvents；Therefore, aqueous photo-curing is overspend
Fluidized polymer has turned into the heat subject in polymer science.
Tang Liming etc. with trimethylolpropane and 2,2 1 dihydromethyl propionic acids is raw material, excessive maleic anhydride changes
Property has synthesized photocuring dissaving polymer；Niu Jianting etc. utilizes the double bond containing compounds such as acryloyl chloride, maleic anhydride
Chemical modification is carried out to over-expense compound, obtains the functional hyperbranched compound that end group is double bond；The virgin firm grade of body is by overspending
Fluidized polymer and GMA react, and introduce double bond, obtain can U V solidifications coating resin.
Wang Xiaoke etc. carries out chemical end modification with TDI to over-expense compound, the acryloyl group containing end is made, the light of carboxyl is consolidated
Change aqueous hyperbranched polyester, then neutralized with NaOH into salt, for emulsion polymerization, anionic self-emulsifying emulsions can be formed.But TDI
Severe poisonous chemicals, chemical property is very active, and volatility is high, and vapour pressure be 3.3Pa at 25 DEG C, saturated vapor concentration for 30 ×
10-6, there is strong impulse smell and lacrimation, respiratory system is stimulated after suction, cause dry cough laryngalgia to suck for a long time micro-
Amount diisocyanate will cause headache bronchitis, and serious meeting causes death, and environment is caused seriously to pollute；International cancer
The in vitro test that research institution (IARC) is carried out shows that TDI can cause the DNA Injury and chromosome aberration grinding tooth of people
Zooblast gene mutation and Sister chromatid exohange, it is suspect carcinogen matter.Other TDI resistances to ag(e)ing, are not suitable in room
Outer use.
The content of the invention
In order to solve the problems, such as techniques as described above, the present invention takes following technical scheme：The present invention relates to a kind of water-based
HDI modified poly ester light-cured resins, by weight percentage, consisting of：The acrylic acid of hyper-branched polyester 1~3%, hydroxyl
Monomer 5~12%, HDI trimer 10~16%, dibutyl tin laurate 0.02~0.3%, cis-butenedioic anhydride 12~25%, N, N- bis-
Methylaniline 5~10%, sodium hydroxide 3~6%, deionized water 40~60%；Described hyper-branched polyester, by weight percentage
Meter, consisting of：2,2- dihydromethyl propionic acids 10~25%, trimethylolpropane 1~4%, p-methyl benzenesulfonic acid 0.1~
0.5%；The acrylic monomers of described hydroxyl is acrylic acid -2- hydroxyl ethyl esters, 2-ethylhexyl acrylate, acrylic acid -2- hydroxyls
Propyl ester, acrylic acid -2- hydroxy butyl esters, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate, methacrylic acid -2- hydroxyls
At least one of butyl ester.
A kind of preparation method of water-based HDI modified poly esters light-cured resin of present invention proposition, its preparation technology, including it is as follows
Step：
A, in a kettle, 2,2- dihydromethyl propionic acids and trimethylolpropane are added by formula ratio, are passed through nitrogen protection,
130 DEG C are warming up to, the catalyst p-methyl benzenesulfonic acid of formula ratio is added, nitrogen is closed after insulation reaction 4h, is continued after reacting 2h,
40 DEG C are cooled to, hyper-branched polyester is made, it is standby；
B, in a kettle, HDI trimer and catalyst dibutyltin dilaurylate are added by formula ratio, it is warming up to 30~
40 DEG C, the acrylic monomers of the hydroxyl measured is added dropwise under agitation, starts sampling detection isocyanide acid number after reacting 0.5h, with
Per 0.5h, sampling once, when detecting the half that isocyanide acid number is initial value, is prepared hyperbranched by formula ratio addition step a afterwards
Polyester, and be warming up to 50~60 DEG C, when continuing reaction to isocyanide acid number and being less than 1%, be warming up to 70~80 DEG C, when isocyanide acid number without
When method is measured, the next step is carried out；
C, the butanone measured is added in b step reactor to be dissolved, while adds the N of formula ratio, N- dimethyl
Aniline, 80 DEG C are warming up to, 50% cis-butenedioic anhydride butanone solution are added dropwise, it is 1h to control time for adding；After being added dropwise, often react 1h and start
Detection architecture acid number is sampled, when detection architecture acid number is the half of initial value, is cooled to 50 DEG C；Add NaOH neutralization reactions
0.5h, deionized water (it is 30~40% to adjust solid content) is added, reduced vacuum extracts butanone out, and one kind is made in agitation and filtration packaging
The water-based HDI modified poly esters light-cured resin of milky.
Water-based HDI modified poly esters light-cured resin produced by the present invention, excellent storage stability；In the presence of light trigger
Film has excellent water resistance, hardness, resistance to ag(e)ing, resistance toization moral character and stain resistance, while also has glossiness high, wear-resisting
The features such as property is good, adhesive force is strong, richness is high, excellent impact resistance, is widely used in woodenware, metal, kirsite, aluminium alloy, magnesium
The surface emissivity application of the products such as alloy, plastics and protection.
Embodiment
Embodiment 1：
A, in a kettle, 18 parts of 2,2- dihydromethyl propionic acids and 2 parts of trimethylolpropanes are added, are passed through nitrogen protection,
130 DEG C are warming up to, 0.2 part of p-methyl benzenesulfonic acid is added, nitrogen is closed after insulation reaction 4h, continues after reacting 2h, is cooled to 40
DEG C, hyper-branched polyester is made, it is standby；
B, in a kettle, 12 parts of HDI trimers and 0.06 part of dibutyl tin laurate are added, is warming up to 30~40
DEG C, 5 parts of acrylic acid -2- hydroxyl ethyl ester monomers are added dropwise under agitation, start sampling detection isocyanide acid number after reacting 0.5h, it is later every
0.5h is sampled once, when it is 10.5~11.0% to detect isocyanide acid number to be NCO, adds hyper-branched polyester 2 prepared by step a
Part, and 50~60 DEG C are warming up to, when continuing reaction to isocyanide acid number and being less than 1%, 70~80 DEG C are warming up to, when isocyanide acid number can not
When measuring, the next step is carried out；
C, 4 parts of butanone are added in b step reactor to be stirred, after dissolving completely, add 6 parts of N, N- dimethyl benzenes
Amine, 80 DEG C are warming up to, 28 parts of 50% cis-butenedioic anhydride butanone solution are added dropwise, it is 1h to control time for adding；After being added dropwise, often react 1h and open
Begin sampling detection architecture acid number, when system acid number is 10~11mgKOH/g, is cooled to 50 DEG C；Add 4 parts of NaOH neutralization reactions
0.5h, 52 parts of deionized waters are added, reduced vacuum extracts butanone out, and it is 41.6% breast that a kind of solid content, which is made, in agitation and filtration packaging
White water-borne HDI modified poly ester light-cured resins.
Embodiment 2：
A, hyper-branched polyester in example 1 with reference to having step a；
B, in a kettle, 11 parts of HDI trimers and 0.06 part of dibutyl tin laurate are added, is warming up to 30~40
DEG C, 6 parts of 2-hydroxypropyl acrylate monomers are added dropwise under agitation, start sampling detection isocyanide acid number after reacting 0.5h, it is later every
0.5h is sampled once, when it is 10.5~11.0% to detect isocyanide acid number to be NCO, adds hyper-branched polyester 1.6 prepared by step a
Part, and 50~60 DEG C are warming up to, when continuing reaction to isocyanide acid number and being less than 1%, 70~80 DEG C are warming up to, when isocyanide acid number can not
When measuring, the next step is carried out；
C, 4 parts of butanone are added in b step reactor to be stirred, after dissolving completely, add 5.6 parts of N, N- dimethyl benzenes
Amine, 80 DEG C are warming up to, 26 parts of 50% cis-butenedioic anhydride butanone solution are added dropwise, it is 1h to control time for adding；After being added dropwise, often react 1h and open
Begin sampling detection architecture acid number, when system acid number is 10~11mgKOH/g, is cooled to 50 DEG C；Add in 3.5 parts of NaOH and anti-
0.5h is answered, adds 48 parts of deionized waters, reduced vacuum extracts butanone out, and it is 42.2% that a kind of solid content, which is made, in agitation and filtration packaging
The water-based HDI modified poly esters light-cured resin of milky.
Embodiment 3：
Water-based HDI modified poly esters light-cured resin made from the embodiment of the present invention is configured to water-based UV varnish, formula is such as
Under：Water-based 60~65 parts of HDI modified poly esters light-cured resin, 4.5 parts of light trigger, 0.2 part of defoamer, substrate wetting agents 0.3
Part, 0.2 part of levelling agent, deionized water is mended to 100；Above-mentioned formula is pressed with water-based TDI modified poly esters light-cured resin (comparative example)
Water-based UV varnish is made, contrast test, film radiation curing 10s, test knot are carried out to film performance according to relevant national standard
Fruit is as shown in table 1.
Table 1：Film performance test result
Although the present invention has been explained in detail and has been cited embodiment, for one of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of claim.
Claims (2)
- A kind of 1. water-based HDI modified poly esters light-cured resin, it is characterised in that：Described water-based HDI modified poly esters photocuring tree Fat, prepared by following steps：A, in a kettle, 18 parts of 2,2- dihydromethyl propionic acids and 2 parts of trimethylolpropanes are added, are passed through nitrogen protection, heating To 130 DEG C, 0.2 part of p-methyl benzenesulfonic acid is added, nitrogen is closed after insulation reaction 4h, continued after reacting 2h, be cooled to 40 DEG C, system Obtain hyper-branched polyester；B, in a kettle, 12 parts of HDI trimers and 0.06 part of dibutyl tin laurate are added, is warming up to 30~40 DEG C, Stirring is lower to be added dropwise 5 parts of acrylic acid -2- hydroxyl ethyl ester monomers, starts sampling detection isocyanide acid number after reacting 0.5h, is taken later per 0.5h Sample once, when it is 10.5~11.0% to detect isocyanide acid number to be NCO, adds 2 parts of step a hyper-branched polyesters, and be warming up to 50 ~60 DEG C, continue reaction to isocyanide acid number be less than 1% when, be warming up to 70~80 DEG C；When isocyanide acid number can not be measured, 4 are added Part butanone, after stirring and dissolving is complete, 6 parts of DMAs are added, are warming up to 80 DEG C, 50% cis-butenedioic anhydride butanone solution 28 is added dropwise Part, it is 1h to control time for adding；After being added dropwise, often react 1h start sample detection architecture acid number, when system acid number be 10~ During 11mgKOH/g, 50 DEG C are cooled to；4 parts of NaOH neutralization reaction 0.5h are added, add 52 parts of deionized waters, reduced vacuum is extracted out Butanone, it is the water-based HDI modified poly esters light-cured resin of 41.6% milky that a kind of solid content, which is made, in agitation and filtration packaging.
- A kind of 2. water-based HDI modified poly esters light-cured resin, it is characterised in that：Described water-based HDI modified poly esters photocuring tree Fat, prepared by following steps：A, in a kettle, 18 parts of 2,2- dihydromethyl propionic acids and 2 parts of trimethylolpropanes are added, are passed through nitrogen protection, heating To 130 DEG C, 0.2 part of p-methyl benzenesulfonic acid is added, nitrogen is closed after insulation reaction 4h, continued after reacting 2h, be cooled to 40 DEG C, system Obtain hyper-branched polyester；B, in a kettle, 11 parts of HDI trimers and 0.06 part of dibutyl tin laurate are added, is warming up to 30~40 DEG C, Stirring is lower to be added dropwise 6 parts of 2-hydroxypropyl acrylate monomers, starts sampling detection isocyanide acid number after reacting 0.5h, is taken later per 0.5h Sample once, when it is 10.5~11.0% to detect isocyanide acid number to be NCO, adds 1.6 parts of step a hyper-branched polyesters, and be warming up to 50~60 DEG C, continue reaction to isocyanide acid number be less than 1% when, be warming up to 70~80 DEG C；When isocyanide acid number can not be measured, add 4 parts of butanone, after stirring and dissolving is complete, 5.6 parts of DMAs are added, are warming up to 80 DEG C, it is molten that 50% cis-butenedioic anhydride butanone is added dropwise 26 parts of liquid, it is 1h to control time for adding；After being added dropwise, often react 1h and start to sample detection architecture acid number, when system acid number is During 10~11mgKOH/g, 50 DEG C are cooled to；3.5 parts of NaOH neutralization reaction 0.5h are added, add 48 parts of deionized waters, decompression is true Sky extracts butanone out, and it is the water-based HDI modified poly esters photocuring tree of 42.2% milky that a kind of solid content, which is made, in agitation and filtration packaging Fat.
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| CN108641515B (en) * | 2018-05-28 | 2020-10-27 | 湖南松井新材料股份有限公司 | High-adhesion primer coating |
| CN110669202A (en) * | 2019-10-18 | 2020-01-10 | 南雄市沃太化工有限公司 | Light-curable aqueous hyperbranched resin and preparation method thereof |
| CN115286946A (en) * | 2022-08-29 | 2022-11-04 | 湖南怡美新材料科技有限公司 | Environment-friendly two-component water-based wood paint and preparation method thereof |
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| CN102030884A (en) * | 2010-10-26 | 2011-04-27 | 华南理工大学 | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof |
| CN102225992A (en) * | 2011-04-22 | 2011-10-26 | 烟台德邦电子材料有限公司 | Photocuring resin and preparation method thereof |
| CN102585158A (en) * | 2011-12-23 | 2012-07-18 | 江苏飞翔化工股份有限公司 | Water-based double-component light-cured polyurethane resin and preparation method thereof |
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| CN102030884A (en) * | 2010-10-26 | 2011-04-27 | 华南理工大学 | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof |
| CN102225992A (en) * | 2011-04-22 | 2011-10-26 | 烟台德邦电子材料有限公司 | Photocuring resin and preparation method thereof |
| CN102585158A (en) * | 2011-12-23 | 2012-07-18 | 江苏飞翔化工股份有限公司 | Water-based double-component light-cured polyurethane resin and preparation method thereof |
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